CN104211840B - A low toxicity emulsifier for producing a fluoropolymer, and a polymerization reaction of a fluorine-containing - Google Patents

A low toxicity emulsifier for producing a fluoropolymer, and a polymerization reaction of a fluorine-containing Download PDF

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CN104211840B
CN104211840B CN 201310218786 CN201310218786A CN104211840B CN 104211840 B CN104211840 B CN 104211840B CN 201310218786 CN201310218786 CN 201310218786 CN 201310218786 A CN201310218786 A CN 201310218786A CN 104211840 B CN104211840 B CN 104211840B
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emulsifier
fluorine
polymerization
containing
low toxicity
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CN104211840A (en )
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夏俊
张宝亮
马鹏飞
魏文涛
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山东东岳高分子材料有限公司
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本发明涉及一种含氟聚合反应的低毒性乳化剂及含氟聚合物的制备方法。 The present invention relates to low toxicity emulsifier for producing a fluoropolymer and a fluorine-containing polymerization. 该乳化剂是由全氟庚酸或全氟庚酸盐提纯制得,通式为CF3(CF2)5COOM,M为H、Li、Na、K或NH4离子中的一种;其中,结构为CF3(CF2)nCOOM(n≥6的整数)的杂质总含量≤1wt%,且结构为CF3(CF2)mCOOM(0≤m≤4的整数)的杂质总含量≤1wt%。 The emulsifier is prepared from perfluoro heptanoic acid or perfluoro heptanoate purification system, the formula CF3 (CF2) 5COOM, M is H, Li, Na, K or one NH4 ions; wherein the structure is CF3 total content of impurities (CF2) nCOOM (n≥6 integer) is ≤1wt%, and the structure of CF3 (CF2) mCOOM (integer of 0≤m≤4) of total impurities ≤1wt%. 本发明含氟聚合反应的低毒性乳化剂可应用于各种含氟聚合反应生产含氟聚合物。 The fluorine-containing emulsifier of the present invention of low toxicity may be applied to the polymerization reaction to produce a variety of fluorine-containing polymeric fluoropolymers. 本发明还提供含氟聚合物的制备方法。 The present invention also provides a method of preparing a fluoropolymer. 本发明含氟聚合反应的乳化剂生物毒性低,聚合反应时间短,含氟聚合物乳液稳定性高,含氟聚合物分子量高,色度好,粒径合适,标准比重小。 The fluorine-containing emulsifier of the present invention is of low toxicity of the polymerization reaction, the polymerization reaction time is short, high fluoropolymer emulsion stability, a high molecular weight fluoropolymer, good color, proper particle size, small standard specific gravity.

Description

一种含氟聚合反应的低毒性乳化剂及含氟聚合物的制备方法 A low toxicity emulsifier for producing a fluoropolymer, and a polymerization reaction of a fluorine-containing

技术领域 FIELD

[0001] 本发明涉及一种含氟聚合反应的低毒性乳化剂及含氟聚合物的制备方法,属于含氟聚合物合成技术领域。 [0001] The present invention relates to low toxicity emulsifier for producing a fluoropolymer and a fluorine-containing polymerization, synthetic techniques belonging to the field of fluoropolymer.

背景技术 Background technique

[0002] 乳化剂是分散法生产含氟聚合物领域中重要的试剂。 [0002] The emulsifier is important in the production of the fluoropolymer art agent dispersion method. 在生产过程中,含氟聚合物乳液的初级粒子粒径尤为重要,粒径过小的粒子在含氟聚合物乳液凝聚过程中难以析出,并且容易导致树脂挤出时压力过高,粒径过大的粒子会导致反应体系不稳定,导致含氟聚合物乳液提前凝聚析出。 In the production process, the primary particle diameter of emulsion of fluorine-containing polymer is particularly important, the particle size is too small it is difficult to precipitate particles in the fluoropolymer emulsion aggregation process, and prone to resin extrusion pressure is too high, the particle size is too large particles can cause a reaction system unstable, resulting fluorine-containing polymer emulsion aggregation advance precipitation. 加入一定量的乳化剂能有效的调控乳液的初级粒子粒径,并能使初级粒子粒径处于最优的范围内。 Adding an amount of emulsifier effective regulation of primary particle diameter of the emulsion, and enables a primary particle diameter is within the optimal range.

[0003] 分散法生产含氟聚合物领域应用最为广泛的含氟表面活性剂是全氟辛酸,SPC7F15C00H及其衍生物,或称为“C8”,是一种人工合成而非天然存在的工业原料。 [0003] Field of the fluoropolymer dispersion production of the most widely used fluorinated surfactants are perfluorooctanoic acid, SPC7F15C00H and derivatives thereof, or referred to as "C8", it is a synthetic, not naturally occurring industrial raw materials. 全氟辛酸铵(PF0A)的分子结构在赋予其优良表面性能的同时,也注定了其在环境中的持久性与累积性。 Ammonium perfluorooctanoate (PF0A) in the molecular structure thereof while giving excellent surface properties, but also determines its persistence in the environment and accumulation of. 因为PF0A分子中含有全氟基团,且相互连接的碳链比较长,最终导致PF0A具有强的热稳定性和动力学稳定性,增加了PF0A分子在环境中的持久性。 Because PF0A containing perfluoro groups in the molecule, and each carbon chain is relatively long, resulting in a strong PF0A dynamic stability and thermal stability, increased persistence PF0A molecules in the environment. 经研究表明,PF0A在经受强热、光照、化学作用、微生物作用和高等脊椎动物的代谢作用下均很难降解,PF0A是目前世界上发现的最难降解的有机污染物之一。 The study shows that, PF0A subjected are difficult to degrade under the intense heat, light, chemical action, and the action of microorganisms metabolism of higher vertebrates, PF0A one organic pollutants found in the world the most recalcitrant. 目前一些发达国家和非政府组织已将PF0A对环境及人体健康可能造成的危害作为热点进行关注。 At present, some developed countries and non-governmental organizations have PF0A harm the environment and human health are likely to cause concern as a hot spot.

[0004]目前国内外许多氟化工生产厂家都在积极开发PF0A的替代品,并开展了大量工作。 [0004] Currently many domestic and foreign fluorine chemical manufacturers are actively developing PF0A alternatives, and carried out a lot of work. 例如:中昊晨光化工研究院在中国专利文献CN101648122A (申请号200910092202.2)中采用含氟烯烃在低温下由氧气氧化制备含醚链段的表面活性剂;但是,这种方法得到的表面活性剂含有大量的支链,在聚合过程中分散性不好。 For example: Research Institute of Chemical Hao dawn fluorine-containing olefin in the low temperature surfactant containing ether segments prepared by the oxidation by oxygen in the Chinese patent document CN101648122A (Application No. 200910092202.2); however, the surfactant obtained in this manner contains a large number of branches, during polymerization poor dispersion. 巨化集团公司在中国专利文献CN102504063A (申请号201110338501)中采用含氯原子的含氟醚链段的表面活性剂,但此表面活性剂的毒性较大,不能完全满足环境友好的要求。 Giant Group employed in China Patent Document CN102504063A (Application No. 201110338501) fluoroether surfactant segments chlorine atoms, but the high toxicity of this surfactant can not fully meet the requirements of environment-friendly. 美国专利文献US5789508,US4025709,US5688884,US5763552等提到的表面活性剂,由于分子结构的关系,在聚合反应过程中会影响聚合物的产品质量。 U.S. Patent Document US5789508, US4025709, US5688884, US5763552 and other surfactants mentioned, the relationship between molecular structure, during the polymerization reaction will affect the quality of the polymer product. 在专利W02005/042593提到采用CF3 (CF2) 5C00NH4作为C8的替代品,用于分散法制备PTFE,但是由于分散体系的稳定性不好,只得到了初级粒径较大且相对分子质量较小的物料,产品SSG大于2.2。 Patent W02005 / 042593 mentioned using CF3 (CF2) 5C00NH4 C8 as a substitute for Preparation of dispersion PTFE, but due to poor stability of the dispersion system, only a small primary particle size was larger and relative molecular mass materials, products SSG greater than 2.2.

发明内容 SUMMARY

[0005] 针对现有技术的不足,本发明提供一种含氟聚合反应的低毒性乳化剂及含氟聚合物的制备方法。 [0005] for the deficiencies of the prior art, the present invention provides a low toxicity and an emulsifier for producing a fluoropolymer polymerization of a fluorine.

[0006]目前使用的CF3 (CF2) 5C00M化合物并不纯净,含有较多杂质,影响了含氟聚合反应的稳定性,聚合反应时间较长,制备的含氟聚合物粒径较差、标准比重(SSG)较高。 [0006] Currently used CF3 (CF2) 5C00M compound is not pure, containing impurities, affecting the stability of the fluorine-containing polymerization reaction, longer polymerization time, poor fluoropolymer particle prepared in the standard specific gravity (SSG) high.

[0007] 本发明人经长期研究意外地发现CF3(CF2)5C00M化合物(Μ为H、L1、Na、K或順4,优选Η或NH4)中杂质种类和含量对于分散法制备出的含氟聚合物性能和乳化剂本身生物毒性有影响,采用纯度高、特定杂质少的cf3 (cf2) 5coom化合物作为乳化剂,得到了分子量高,乳液初级粒径合适,标准比重(SSG)较好的含氟聚合物。 [0007] The present inventors have unexpectedly found that CF3 (CF2) 5C00M compound ([mu] is H, L1, Na, K or cis-4, or preferably Η NH4) kind and content of impurities in the prepared dispersion method for the long-term study of fluorine emulsifying properties of the polymer itself and affect toxicity, high purity, low specific impurities cf3 (cf2) 5coom compound as an emulsifier, to obtain a high molecular weight, primary particle size of the emulsion suitable, standard specific gravity (SSG) preferably containing fluoropolymer.

[0008] 本发明的技术方案如下: [0008] The aspect of the present invention is as follows:

[0009] —种含氟聚合反应的低毒性乳化剂,该乳化剂是由全氟庚酸或全氟庚酸盐提纯制得,通式为CF3 (CF2) 5C00M,Μ为H、L1、Na、K或NH4离子中的一种;其中,结构为CF 3 (CF2) nC00M(η彡6的整数)的杂质总含量彡lwt%,且结构为CF3(CF丄C00M (0彡m彡4的整数)的杂质总含量< lwt%。 [0009] - low toxicity polymerization fluorine-containing emulsifier, the emulsifier is made from perfluoro heptanoic acid or perfluoro heptanoate purification system, the formula CF3 (CF2) 5C00M, Μ is H, L1, Na , K or NH4 ions one; wherein the total content of impurity structure CF 3 (CF2) nC00M (η 6 San integer) of San lwt%, and the structure CF3 (CF Shang C00M (0 m San San 4 integer) total impurities <lwt%.

[0010] 乳化剂中CF3(CF2)nC00M (η彡6的整数)结构的杂质是带来生物毒性的主要原因,如果乳化剂中CF3(CF2)nC00M (η ^ 6的整数)结构的杂质总含量> lwt%,乳化剂的生物毒性将不能忽略,甚至不能用作含氟聚合反应的乳化剂。 [0010] The emulsifier CF3 (CF2) nC00M (η 6 San integer) impurity structure is to bring the main reason for the toxicity, if the impurity emulsifier CF3 (CF2) nC00M (η ^ 6 of an integer) of the total structure content of> lwt%, emulsifier toxicity can not be ignored, can not even be used as the fluorinated polymeric emulsifier reactions. 乳化剂中CFjCFj^COOiKO彡m彡4的整数)结构的各种杂质是影响含氟聚合物产品性能的主要原因,如果乳化剂中CF3(CF2)nC00M (0彡m彡4的整数)结构的杂质总含量> lwt%,乳化剂的表面活性将会降低,甚至不能作为乳化剂用于含氟聚合物的制备,此外还会增加含氟聚合反应体系的凝聚倾向、延长反应时间、降低含氟聚合物的分子量等。 Various impurities emulsifiers CFjCFj ^ COOiKO San integer m San 4) Effect of a configuration of the main reasons is the fluorine-containing polymer product properties, if the integer emulsifier CF3 (CF2) nC00M (0 m San San 4) Structure the total content of impurities> lwt%, of a surfactant emulsifier will be reduced, even for the preparation of the emulsifier can not be used as the fluoropolymer, fluorine-containing addition polymerization reaction system will increase aggregation tendency, reaction time, reduced fluorine the molecular weight of the polymer.

[0011] 根据本发明,优选的,所述的乳化剂中结构为CF3(CF2)nC00M(n ^ 6的整数)的杂质总含量彡0.5wt%,更优选彡0.lwt% ;并且所述的乳化剂中结构为CFjCF^mCOOiKO彡m彡4的整数)的杂质总含量< 0.5wt%,更优选< 0.lwt%。 The total content of impurities San [0011] According to the present invention, preferably, the emulsifier in the structure (the integer n ^ 6) CF3 (CF2) nC00M of 0.5wt%, more preferably San 0.lwt%; and the the emulsifiers structure CFjCF ^ mCOOiKO San San integer m. 4) total content of impurities <0.5wt%, more preferably <0.lwt%.

[0012] 根据本发明,所述的乳化剂中碘和碘化合物总含量<50ppm,优选碘和碘化合物总含量< lOppm,更优选碘和碘化合物总含量< lppm。 [0012] According to the invention, the total content of the emulsifier iodine and iodine compounds <50ppm, preferably iodine and iodine compounds the total content of <lOppm, the total content is more preferably iodine and iodine compounds <lppm.

[0013] 如果乳化剂中碘和碘化合物总含量过高,将会延长含氟聚合反应体系的反应时间、降低含氟聚合物的分子量,还会影响含氟聚合物的色度。 [0013] If the total content of emulsifier is too high iodine and iodine compound, polymerization reaction time will be extended fluorine reaction system, reduce the molecular weight of the fluoropolymer, the fluoropolymer also affects the color.

[0014] 本发明采用公知的方法对乳化剂化合物CF3 (CF2) 5C00M进行提纯,如通过蒸馏、精馏等方法脱除乳化剂中结构为CF3(CF2)nC00M(n ^ 6的整数)的各种杂质和结构为CF3(CF2)mC00M (0 ^ m ^ 4的整数)的各种杂质。 [0014] The method of the present invention is a known compound emulsifier CF3 (CF2) 5C00M purified, as by distillation to remove the emulsifier structure, a method such as distillation (the integer n ^ 6) CF3 (CF2) nC00M each impurity and structure CF3 (CF2) mC00M (^ m ^ integer of 0 4) of various impurities. 碘和碘化合物杂质的提纯方法优选通过使用还原性Na2S2(VK溶液洗涤进行脱除。 Iodine and iodine compound impurities removed by the purification process is preferably carried out using a reducing washed Na2S2 (VK solution.

[0015] 本发明,优选的,对乳化剂化合物CF3 (CF2) 5C00M提纯的步骤如下: [0015] In the present invention, preferably, the step of emulsifying the compound CF3 (CF2) 5C00M purified as follows:

[0016] (1)对全氟庚酸或全氟庚酸盐用0.01〜lmol/L的Na2S2(yK溶液反复洗涤至碘和碘化合物总含量< 50ppm ;更优选,碘和碘化合物总含量< lppm ; [0016] (1) (yK solution was washed on perfluoroheptanoic acid or perfluoro heptanoate with 0.01~lmol L of Na2S2 / repeated to a total iodine compound and an iodine content <50 ppm; the total content is more preferably, iodine and iodine compound < lppm;

[0017] (2)然后对全氟庚酸或全氟庚酸盐进行精馏,在精馏塔顶30mmHg压力、100〜102°C下收集塔顶物料,即得,本发明含氟聚合反应的低毒性乳化剂。 [0017] (2) Then perfluoroheptanoic acid or perfluoro heptanoate rectified in the rectification column top pressure of 30mmHg, the material collected overhead at 100~102 ° C, to obtain the fluorine-containing polymerization reaction of the present invention low toxicity emulsifier.

[0018] 本发明含氟聚合反应的低毒性乳化剂可应用于各种含氟聚合反应生产含氟聚合物,特别适合作为乳化剂生产聚四氟乙烯、四氟乙烯与其他全氟烯烃共聚物,如六氟丙烯、全氟烷基乙烯基醚共聚物等。 [0018] The fluorine-containing emulsifier of the present invention is low in toxicity may be applied to the polymerization reaction to produce a variety of fluorine-containing polymeric fluoropolymers are particularly suitable as emulsifiers produce polytetrafluoroethylene, tetrafluoroethylene copolymers with other perfluoroolefins , such as hexafluoropropylene, perfluoroalkyl vinyl ether copolymer and the like.

[0019] —种含氟聚合物的制备方法,步骤如下: [0019] - The method of producing a fluoropolymer of the following steps:

[0020] (1)搅拌条件下向聚合反应釜中加入水、本发明的乳化剂,加热聚合反应釜至50〜150°C,然后加入水重量0.1〜500 ppm的引发剂引发聚合反应; The initiator [0020] (1) with stirring to the polymerization kettle was added water, the emulsifier of the present invention, the polymerization reactor was heated to 50~150 ° C, then water 0.1~500 ppm by weight polymerization initiator;

[0021] 所述的乳化剂加入量为水重量的0.01%〜1% ; Emulsifier according to [0021] added in an amount of 0.01% ~ 1% by weight of water;

[0022] 所述的引发剂包括但不限于:过硫酸铵、过硫酸钾、过氧化叔丁基异丙苯、过氧化苯甲酰、偶氮二异丁腈、高锰酸钾、过氧化琥珀酸、过硫酸钾和亚硫酸钠的氧化还原体系、过硫酸钾和硫酸氢钠和硫酸亚铁的氧化还原体系、过硫酸钾和硫酸氢钠和硝酸银的氧化还原体系; [0022] The initiators include, but are not limited to: ammonium persulfate, potassium persulfate, t-butyl cumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, potassium permanganate, succinic acid peroxide , potassium persulfate and sodium sulfite redox system, potassium persulfate and sodium bisulfite and ferrous sulfate redox system, potassium persulfate and sodium hydrogen sulfate and silver nitrate redox systems;

[0023] (2)连续通入含氟单体维持聚合反应釜压力恒定,所述恒定压力大小为0.3〜7.0MPa ; [0023] (2) a fluorine-containing monomer is continuously introduced into the polymerization reactor to maintain a constant pressure, said constant pressure size 0.3~7.0MPa;

[0024] (3)反应完成后,将反应乳液中的含氟聚合物凝聚分离、水洗涤、干燥,即得固态含氟聚合物; After completion of [0024] (3) the reaction, the emulsion was coagulation washed fluoropolymer separated, water, and dried to obtain a fluorine-containing polymer solid;

[0025] 或者,对反应完的乳液进行浓缩,至浓缩液中含氟聚合物的浓度为30%〜70wt%,即得含氟聚合物浓缩液。 [0025] Alternatively, the emulsion was concentrated completion of the reaction, the concentration of the fluoropolymer solution was concentrated to 30% ~70wt%, to obtain a fluoropolymer concentrate.

[0026] 步骤(1)中采用本领域常规搅拌条件即可。 [0026] Step to (1) with stirring in a conventional art.

[0027] 根据本发明,优选的,所述的步骤(1)中加热聚合反应釜之前再加入水重量的0.1〜12%的石蜡; [0027] According to the present invention, preferably, the step of 0.1~12% by weight of paraffin was further added water prior to the polymerization reactor (1) is heated;

[0028] 优选的,加热聚合反应釜之前再加入水重量0.01〜0.1%的丁二酸调节pH ; [0028] Preferably, the heat polymerization 0.01~0.1% by weight of water was added succinic acid the pH is adjusted before the reactor;

[0029] 优选的,加热聚合反应爸之前再加入0.1〜10g辛基酸聚氧乙稀醚,作用为改善聚合反应; [0029] Preferably, the polymerization heat was added 0.1~10g acid polyoxyethylene octyl ether, ethylene before reaction, Dad role in improving the polymerization reaction;

[0030] 优选的,加入引发剂之前反复充入抽出四氟乙烯至聚合反应釜的氧气含量30ppm。 [0030] Preferably, the extraction is added repeatedly charged oxygen content tetrafluoroethylene to the polymerization reactor before the initiator is 30ppm.

[0031] 根据本发明,优选的,所述的步骤(2)中含氟单体为四氟乙烯、偏氟乙烯、三氟氯乙烯、六氟丙烯或全氟烷基乙烯基醚中的一种或几种混合。 [0031] According to the present invention, preferably, the step (2) is a fluorine-containing monomer is tetrafluoroethylene, a vinylidene fluoride, ethylene, chlorotrifluoroethylene, hexafluoropropylene or perfluoroalkyl vinyl ethers several species or mixed.

[0032] 本发明所述的步骤(3)中凝聚分离的方法可以是任何便利的方法,如强烈搅拌,有选择的添加具有低表面张力的电解液和/或不与水混溶的溶剂,冷冻等方法;按本领域常规操作即可; The method of separation step (3) in the present invention agglomerated [0032] may be any convenient method, such as vigorous stirring, optionally with addition of electrolyte and / or water-immiscible solvent with low surface tension, freezing or the like; operation according to the conventional art can;

[0033] 干燥温度为10°C〜250 °C,更优是100 °C〜200 °C。 [0033] The drying temperature is 10 ° C~250 ° C, more preferably is 100 ° C~200 ° C.

[0034] 本发明含氟聚合反应的低毒性乳化剂优选用于分散法制备聚四氟乙烯,步骤如下: [0034] The present invention is a fluorine-containing polymerization emulsifier is preferably a low toxicity polytetrafluoroethylene dispersion method, the steps of:

[0035] —种聚四氟乙烯的制备方法,步骤如下 [0035] - The method of producing PTFE, the following steps

[0036] (1)搅拌条件下向聚合反应釜中加入水、本发明的乳化剂、石蜡、丁二酸和辛基酚聚氧乙烯醚,加热聚合反应釜至50〜150°C, The [0036] (1) with stirring to the polymerization kettle was added water, the emulsifier of the present invention, paraffin, succinic acid and polyoxyethylene octylphenol ether, the polymerization reactor was heated to 50~150 ° C,

[0037] 所述的乳化剂加入量为水重量的0.01%〜1% ; Emulsifier according to [0037] added in an amount of 0.01% ~ 1% by weight of water;

[0038] 所述的石蜡加入量为水重量的0.1〜12% ; [0038] The paraffin wax was added in an amount of 0.1~12% by weight of water;

[0039] 所述的丁二酸加入量为水重量的0.01〜0.1% ; [0039] The succinic acid is added in an amount of 0.01~0.1% by weight of water;

[0040] 所述的辛基酚聚氧乙烯醚加入量为0.7g ; [0040] The polyoxyethylene octylphenol ether was added in an amount of 0.7 g;

[0041] 当温度达到60〜85 °C时,对聚合反应釜进行抽空后,反复充入抽出四氟乙烯(TFE)至聚合反应爸内氧含量彡30ppm ; [0041] When the temperature reached 60~85 ° C, after evacuation of the polymerization reactor, is repeatedly charged out of tetrafluoroethylene (TFE) to the polymerization reaction within 30 ppm or dad San oxygen content;

[0042] 然后加入水重量0.1〜500 ppm的引发剂引发聚合反应; [0042] 0.1~500 ppm by weight of water were then added to initiate polymerization initiator;

[0043] 所述的引发剂包括但不限于:过硫酸铵、过硫酸钾、过氧化叔丁基异丙苯、过氧化苯甲酰、偶氮二异丁腈、高锰酸钾、过氧化琥珀酸、过硫酸钾和亚硫酸钠的氧化还原体系、过硫酸钾和硫酸氢钠和硫酸亚铁的氧化还原体系、过硫酸钾和硫酸氢钠和硝酸银的氧化还原体系; [0043] The initiators include, but are not limited to: ammonium persulfate, potassium persulfate, t-butyl cumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, potassium permanganate, succinic acid peroxide , potassium persulfate and sodium sulfite redox system, potassium persulfate and sodium bisulfite and ferrous sulfate redox system, potassium persulfate and sodium hydrogen sulfate and silver nitrate redox systems;

[0044] (2)连续通入四氟乙烯维持聚合反应釜压力恒定,所述恒定压力大小为0.3〜7.0MPa ; [0044] (2) of tetrafluoroethylene was continuously fed to maintain a constant pressure in the polymerization reactor, the size of the constant pressure 0.3~7.0MPa;

[0045] (3)反应完成后,将反应乳液中的含氟聚合物凝聚分离、水洗涤、100〜200°C干燥,即得固态聚四氟乙烯; After completion of [0045] (3) the reaction, the emulsion fluoropolymer coagulation was separated, washed with water, 100~200 ° C and dried to obtain a solid polytetrafluoroethylene;

[0046] 或者,对反应完的乳液进行浓缩,至浓缩液中含氟聚合物的浓度为30%〜70wt% ;即得聚四氟乙烯浓缩液。 [0046] Alternatively, the emulsion of the completion of the reaction was concentrated, and concentrated to a concentration in the fluorine-containing polymer is 30% ~70wt%; polytetrafluoroethylene to obtain a concentrate.

[0047] 使用本发明的乳化剂分散法合成含氟聚合物时,聚合反应体系的水相中固含量为20〜60%为佳。 [0047] using the method of the present invention when the synthetic emulsifier fluoropolymer dispersion, an aqueous phase polymerization reaction system is preferably a solids content of 20~60%.

[0048] 含氟聚合反应中乳化剂的质量和种类对聚合反应影响巨大,乳化剂中杂质的含量和种类对含氟聚合反应有着重要影响。 [0048] The fluorine-containing emulsifier in the polymerization reaction types and a huge impact on the quality of the polymerization, the emulsifier amount and type of impurities in the polymerization reaction of the fluorine has an important impact. 对于全氟羧酸类乳化剂,碳原子数目少的杂质如果含量较高,乳化剂的表面活性将降低,还会增加聚合反应体系的凝聚倾向、延长反应时间、降低聚合物分子量等,这将严重影响含氟聚合物的制备。 For perfluorocarboxylic acid type emulsifier, a small number of carbon atoms if the impurity content is high, the surface active emulsifier will decrease aggregation tendency will increase the polymerization reaction system, reaction time, reducing polymer molecular weight and the like, which will making a fluoropolymer seriously affected. 对于全氟羧酸类乳化剂,如果碳原子数目多的杂质含量较高,乳化剂的毒性会增加,不符合环保要求,甚至不能使用。 For perfluorocarboxylic acid type emulsifier, if the number of carbon atoms higher number of impurities, will increase the toxicity of the emulsifier, does not meet environmental requirements, can not even be used. 此外,不同的杂质对乳化剂使用效果的影响不同,碘和碘化合物会严重影响乳化剂的质量,碘和碘化合物含量过高,会延长体系的反应时间、降低聚合物分子量,同时会影响聚合物的色度。 Further, different effects on different impurity emulsifier effect, iodine and iodine compound will seriously affect the quality of the emulsifier, iodine and iodine compound content is too high, the reaction time of the system, reducing the polymer molecular weight, the polymerization will also affect chromaticity thereof. 因此,在选择含氟聚合反应的乳化剂时,既要考虑乳化剂的毒性,又要考虑乳化剂对产品性能的影响。 Thus, the fluorine-containing emulsifier in the choice of the polymerization reaction, it is necessary to consider the toxicity of an emulsifier, but also consider the effect of emulsifiers on product performance.

[0049] 本发明通过对全氟庚酸乳化剂中杂质种类和含量的选择研究,提供用于含氟聚合反应且有较好效果的低毒性乳化剂。 [0049] Selection of the present invention by perfluoroheptanoic acid emulsifier type and content of impurities, there is provided a fluorine-containing emulsifier in the polymerization of low toxicity and has better reaction effect.

[0050] 本发明的有益效果如下: [0050] Advantageous effects of the present invention are as follows:

[0051] 1、本发明含氟聚合反应的乳化剂生物毒性低,使用效果好。 [0051] 1, low toxicity fluorine-containing emulsifier of the present invention, the polymerization reaction, good results.

[0052] 2、使用本发明乳化剂分散法制备含氟聚合时,聚合反应时间短,含氟聚合物乳液稳定性尚。 [0052] 2, the present invention is the use of the emulsifier prepared by dispersing fluorine-containing polymer, the polymerization reaction time is short, yet the fluoropolymer emulsion stability.

[0053] 3、使用本发明乳化剂制备出的含氟聚合物分子量高,色度好,粒径合适,标准比重(SSG)小。 [0053] 3, a high emulsifier in the present invention is a fluorine-containing polymer molecular weight, a good color, suitable particle size, the standard specific gravity (SSG) small.

[0054] 4、本发明为优化含氟聚合反应、缩短含氟聚合反应时间、提高含氟聚合物的粒径质量、减小含氟聚合物的标准比重(SSG)等提供了一条新的途径。 [0054] 4, the present invention provides a new way to optimize the polymerization reaction of fluorine, fluorine shorten the polymerization time, improve the quality of the particle size of the fluoropolymer, the fluoropolymer is reduced standard specific gravity (SSG) and the like .

具体实施方式 detailed description

[0055] 下面通过具体实施例对本发明做进一步说明,但不限于此。 [0055] The following specific embodiments of the present invention is further illustrated, but is not limited thereto.

[0056] 应用例1〜5中聚合物乳液粒径采用光子相关光谱法测定,SSG采用ASTM D-4895方法检测。 [0056] Application of the polymer emulsion particle size was determined by Example 1 ~ 5 photon correlation spectroscopy, SSG using ASTM D-4895 method of detection.

[0057] 实施例1〜2和对比例1〜2中所用乳化剂原料为市购全氟庚酸(结构式CF3(CF2)5C00H);通过LC/MS/MS (液相色谱-质谱联用)分析,其中含1.lwt%的全氟辛酸(结构式CF3(CF2)6C00H)和1.5wt%的全氟己酸(结构式CF3(CF2)4C00H)杂质;元素分析表明含碘元素0.01wt%o [0057] Examples 1~2 and Comparative Example 1~2 embodiment emulsifiers used raw materials are commercially perfluoro heptanoic acid (formula CF3 (CF2) 5C00H); by LC / MS / MS (liquid chromatography - mass spectrometry) analysis, wherein the perfluoro-containing 1.lwt% of octanoic acid (formula CF3 (CF2) 6C00H) and 1.5wt% of perfluoro hexanoic acid (formula CF3 (CF2) 4C00H) impurity; elemental analysis showed elemental iodine 0.01wt% o

[0058] 实施例1 [0058] Example 1

[0059] —种含氟聚合反应的低毒性乳化剂,该乳化剂是由全氟庚酸提纯制得,步骤如下: [0059] - low toxicity polymerization fluorine-containing emulsifier, the emulsifier is purified perfluoro heptanoic acid was prepared, the following steps:

[0060] (1)对市购全氟庚酸用0.lmol/L的Na2S2(yK溶液反复洗涤至碘和碘化合物总含量< lppm ; [0060] (1) of commercially available perfluoro heptanoic acid (yK solution was washed repeatedly until the total content of iodine and an iodine compound <lppm with 0.lmol L of Na2S2 /;

[0061 ] (2)然后进行精馏,在精馏塔顶30mmHg压力、101°C下收集塔顶物料,即得。 [0061] (2) followed by distillation at 30mmHg pressure rectification column top, the material collected overhead at 101 ° C, that is, too.

[0062] 分析提纯后的全氟庚酸(结构式CF3 (CF2) 5C00H)的含量为99.0wt%,其中含0.5wt%的全氟辛酸(结构式CF3 (CF2) 6C00H)和0.5wt%的全氟己酸(结构式CF3 (CF2) 4C00H),碘和碘化合物检测不出。 [0062] Analysis of the content of the purified perfluoro heptanoic acid (formula CF3 (CF2) 5C00H) is 99.0wt%, which perfluorooctanoate containing 0.5wt% of (structural formula CF3 (CF2) 6C00H) and 0.5wt% of perfluoro hexanoic acid (formula CF3 (CF2) 4C00H), iodine and iodine compounds can not be detected.

[0063] 实施例2 [0063] Example 2

[0064] —种含氟聚合反应的低毒性乳化剂,该乳化剂是由全氟庚酸提纯制得,步骤如下: [0064] - low toxicity polymerization fluorine-containing emulsifier, the emulsifier is purified perfluoro heptanoic acid was prepared, the following steps:

[0065] (1)对市购全氟庚酸用0.lmol/L的Na2S203水溶液反复洗涤至碘元素的含量50ppm ; [0065] (1) of commercially available perfluoro heptanoic acid washed 0.lmol / L of an aqueous solution of Na2S203 used repeatedly to iodine content of 50 ppm;

[0066] (2)然后进行精馏,在精馏塔顶30mmHg压力、101°C下收集塔顶物料,即得。 [0066] (2) followed by distillation at 30mmHg pressure rectification column top, the material collected overhead at 101 ° C, that is, too.

[0067] 分析提纯后的全氟庚酸(结构式CF3 (CF2) 5C00H)的含量为99.0wt%,其中含0.5wt%的全氟辛酸(结构式CF3 (CF2) 6C00H)和0.5wt%的全氟己酸(结构式CF3 (CF2) 4C00H)。 [0067] Analysis of the content of the purified perfluoro heptanoic acid (formula CF3 (CF2) 5C00H) is 99.0wt%, which perfluorooctanoate containing 0.5wt% of (structural formula CF3 (CF2) 6C00H) and 0.5wt% of perfluoro hexanoic acid (formula CF3 (CF2) 4C00H).

[0068] 对比例1 [0068] Comparative Example 1

[0069] (1)对市购全氟庚酸用0.lmol/L的Na2S203水溶液反复洗涤至碘元素的含量^ lppm ; [0069] (1) of commercially available perfluoro heptanoic acid washed 0.lmol / L of an aqueous solution of Na2S203 used repeatedly to iodine content of ^ lppm;

[0070] (2)然后进行精馏,在精馏塔顶30mmHg压力、100°C下收集塔顶物料。 [0070] (2) followed by distillation, the material collected overhead at the top of the rectification column pressure of 30mmHg, 100 ° C.

[0071] 分析提纯后的全氟庚酸(结构式CF3 (CF2) 5C00H)的含量为98.0wt%,其中含0.5wt%的全氟辛酸(结构式CF3 (CF2) 6C00H)和1.5wt%的全氟己酸(结构式CF3 (CF2) 4C00H),碘和碘化合物检测不出。 [0071] Analysis of the content of the purified perfluoro heptanoic acid (formula CF3 (CF2) 5C00H) is 98.0wt%, which perfluorooctanoate containing 0.5wt% of (structural formula CF3 (CF2) 6C00H) and 1.5wt% of perfluoro hexanoic acid (formula CF3 (CF2) 4C00H), iodine and iodine compounds can not be detected.

[0072] 对比例2 [0072] Comparative Example 2

[0073] (1)对市购全氟庚酸用0.lmol/L的Na2S203水溶液反复洗涤至碘元素的含量^ lppm ; [0073] (1) of commercially available perfluoro heptanoic acid washed 0.lmol / L of an aqueous solution of Na2S203 used repeatedly to iodine content of ^ lppm;

[0074] (2)不进行精馏处理。 [0074] (2) without distillation process.

[0075] 全氟庚酸(结构式CF3 (CF2) 5C00H)中含1.lwt%的全氟辛酸(结构式CF3 (CF2) 6C00H)和1.5wt%的全氟己酸(结构式CF3(CF2)4C00H)。 [0075] perfluoro heptanoic acid (formula CF3 (CF2) 5C00H) perfluorooctanoate containing 1.lwt% (structural formula CF3 (CF2) 6C00H) and 1.5wt% of perfluoro hexanoic acid (Formula CF3 (CF2) 4C00H).

[0076] 毒性试验1 [0076] Toxicity Test 1

[0077] 采用16只雄性SD大鼠分为4组,每组4只,进行毒性试验。 [0077] 16 male SD rats were divided into 4 groups, 4 rats in each group, toxicity testing.

[0078] 将对比例2的全氟庚酸分别按照0、0.1、1.0和10 mg/kg/day的方式连续7天进行口服施用。 [0078] will perfluoro heptanoic acid, respectively, according to Comparative Example 2 0,0.1,1.0 and 10 mg / kg / day for 7 days manner orally administered. 解剖结果表明,投喂量为1.0mg/kg/day及以上的大鼠组出现肝肿大的现象,无可见有害作用水平的投喂量为0.lmg/kg/day。 The results show the anatomy, feeding amount of 1.0mg / kg / day and above phenomenon hepatomegaly group of rats, with no visible ration adverse effect level is 0.lmg / kg / day.

[0079] 毒性试验2 [0079] Toxicity Test

[0080] 将对比例1的全氟庚酸按照毒性试验1的方式进行动物试验,无可见有害作用水平的投喂量为1.0mg/kg/day。 [0080] perfluoroheptanoic acid ratio will be 1 animal testing in the manner of a toxicity test, no observable adverse effect level ration of 1.0mg / kg / day.

[0081] 对比毒性试验1和毒性试验2结果表明,减少全氟辛酸的残留量能显著改善生物毒性。 [0081] Toxicity Test 1 Comparative Test 2 and toxicity results show that reducing the amount of residual perfluoro octanoic acid significantly improved biological toxicity.

[0082] 应用例1 [0082] Application Example 1

[0083] 将实施例1的全氟庚酸与氨水按1:1摩尔比混合得到全氟庚酸铵盐作为乳化剂分散法制备聚四氟乙烯,步骤如下: [0083] Example 1 perfluoro heptanoic acid with ammonia according to embodiment 1: 1 to give a molar ratio of ammonium salt of perfluoro heptane mixture as an emulsifier polytetrafluoroethylene dispersion method, the steps of:

[0084] (1)在体积为2000L带搅拌器的卧式聚合反应釜中,加入1400kg去离子水,2.1kg全氟庚酸铵盐作为乳化剂,l〇〇〇g 丁二酸和60kg石蜡; [0084] (1) in a volume of 2000L with a stirrer, horizontal polymerization reactor was added deionized water 1400kg, 2.1kg of ammonium perfluoro heptane as an emulsifier salt, succinic acid and 60kg paraffin l〇〇〇g ;

[0085] 加热聚合反应釜,当温度达到65°C时,对聚合反应釜进行抽空后,充入四氟乙烯(TFE)至微正压,反复抽空充压至聚合反应釜内氧含量小于30ppm ; [0085] The polymerization reactor was heated, when the temperature reaches 65 ° C, after the polymerization reaction vessel was evacuated, charged with tetrafluoroethylene (TFE) to a slight positive pressure, again evacuated pressurized into the polymerization reactor an oxygen content of less than 30ppm ;

[0086] 加入0.7g辛基酚聚氧乙烯醚,充入四氟乙烯(TFE)至2.7MPa ;将1.0g过硫酸铵溶于1000ml去离子水,以100ml/min的速度加入聚合反应釜; [0086] Add to 0.7g polyoxyethylene octylphenol ethers, charged with tetrafluoroethylene (TFE) to 2.7MPa; to 1.0g of ammonium persulfate dissolved in 1000ml deionized water at a rate of 100ml / min is added to the polymerization reactor;

[0087] (2 )聚合反应开始后,连续通入四氟乙烯(TFE )维持压力2.7MPa恒定; After the start of [0087] (2) the polymerization reaction, tetrafluoroethylene was continuously fed (TFE) to maintain a constant pressure of 2.7MPa;

[0088] (3)反应完成后,将反应完的乳液中的聚四氟乙烯凝聚分离、水洗涤、干燥,得470kg聚四氟乙烯分散树脂。 After completion of [0088] (3) the reaction, the completion of the reaction the emulsion in a polytetrafluoroethylene coagulation washing the separated, water, and dried to give 470kg polytetrafluoroethylene resin dispersion.

[0089] 本应用例的反应时间为2.lh,反应完成后的乳液浓度为25.3wt%、乳液粒径为290nm,乳液中未有明显的凝聚物。 [0089] The reaction time of the present application example is 2.lh, after completion of the reaction the emulsion concentration was 25.3wt%, the emulsion particle diameter was 290nm, the emulsion No obvious coagulum. 凝聚出来的聚四氟乙烯分散树脂粒子大小为580微米,SSG 为2.158〇 Condensed out polytetrafluoroethylene dispersion resin particle size of 580 microns, SSG is 2.158〇

[0090] 应用例2 [0090] Application Example 2

[0091 ] 将对比例1的全氟庚酸与氨水按1:1摩尔比混合得到全氟庚酸铵盐作为乳化剂分散法制备聚四氟乙烯,步骤如下: [0091] perfluoroheptanoic acid of Comparative Example 1 with ammonia is 1: 1 to give a molar ratio of ammonium salt of perfluoro heptane mixture prepared as emulsifiers dispersing polytetrafluoroethylene Method, the following steps:

[0092] (1)、(2)同应用例1 ; [0092] (1), (2) with Application Example 1;

[0093] (3)反应结束后聚合反应釜内有20kg凝聚物;把凝聚物过滤后,将反应完的乳液中的聚四氟乙烯凝聚分离,经水洗涤、干燥后,得到450kg聚四氟乙烯分散树脂。 [0093] (3) After completion of the polymerization reaction with a reaction kettle 20kg coagulum; the agglomerate was filtered after the completion of the reaction the emulsion in a polytetrafluoroethylene coagulation was separated, washed with water, and dried to obtain PTFE 450kg vinyl dispersion resin.

[0094] 本应用例的反应时间为2.8h,反应完成后的乳液浓度为24.9wt%、乳液粒径310nm。 [0094] The reaction time of the present embodiment is applied 2.8h, after completion of the reaction the emulsion concentration was 24.9wt%, the emulsion particle diameter of 310nm. 凝聚出来的聚四氟乙烯分散树脂粒子大小为630微米,SSG为2.165。 Condensed out polytetrafluoroethylene dispersion resin particle size of 630 microns, SSG of 2.165.

[0095] 对比应用例1和应用例2可知,减少了全氟己酸可使聚合反应的稳定性更好。 [0095] Application Example 1 Comparative Application Example 2 and found to reduce the perfluorohexanoic acid can better polymerization stability.

[0096] 应用例3 [0096] Application Example 3

[0097] 将对比例2的全氟庚酸与氨水按1:1摩尔比混合得到全氟庚酸铵盐作为乳化剂分散法制备聚四氟乙烯,步骤如下: [0097] perfluoroheptanoic acid of Comparative Example 2 with ammonia of 1: 1 to give a molar ratio of ammonium salt of perfluoro heptane mixture prepared as emulsifiers dispersing polytetrafluoroethylene Method, the following steps:

[0098] (1)、(2)同应用例1 ; [0098] (1), (2) with Application Example 1;

[0099] (3)反应结束后,将反应完的乳液中的聚四氟乙烯凝聚分离,经水洗涤、干燥后,得到460kg聚四氟乙烯分散树脂。 After [0099] (3) the reaction, the completion of the reaction in emulsion aggregation polytetrafluoroethylene separated, washed with water, and dried, to give 460kg polytetrafluoroethylene dispersion resin.

[0100] 本应用例的反应时间为3h,反应完成后的乳液浓度25wt%。 The reaction time [0100] according to the present embodiment is applied 3h, an emulsion after the completion of the reaction the concentration of 25wt%. 凝聚出来的粒子大小600 微米,SSG 为2.161。 Out agglomerated particle size 600 microns, SSG of 2.161.

[0101] 应用例4 [0101] Application Example 4

[0102] 将未做任何处理的市购的全氟庚酸与氨水按1:1摩尔比混合得到全氟庚酸铵盐作为乳化剂分散法制备聚四氟乙烯,步骤如下: [0102] The process of making any commercially available perfluoro heptanoic acid with ammonia of 1: 1 to give a molar ratio of ammonium salt of perfluoro heptane mixture prepared as emulsifiers dispersing polytetrafluoroethylene Method, the following steps:

[0103] (1)、(2)同应用例1 ; [0103] (1), (2) with Application Example 1;

[0104] (3)反应结束后聚合反应爸内有20kg凝聚物;把凝聚物过滤后,将反应完的乳液中的聚四氟乙烯凝聚分离,经水洗涤、干燥后,得到250kg聚四氟乙烯分散树脂。 [0104] (3) After completion of the polymerization reaction the reaction has 20kg coagulum dad; after the aggregates by filtration, the completion of the reaction in emulsion aggregation polytetrafluoroethylene separated, washed with water, and dried to obtain PTFE 250kg vinyl dispersion resin.

[0105] 本应用例的反应时间为4.5h,反应完成后的乳液浓度为15.3wt%。 The reaction time [0105] according to the present embodiment is applied 4.5h, after completion of the reaction the emulsion concentration was 15.3wt%.

[0106] 对比应用例4和应用例1、2、3可知,脱除了碘和碘化合物后聚合反应速度大幅提尚。 [0106] Application Example Comparative Application Example 2, 3 and 4 can be seen, in addition to the removal of iodine and iodine compounds mentioned polymerization reaction rate significantly yet.

[0107] 应用例5 [0107] Application Example 5

[0108] 将实施例1的全氟庚酸与氨水按1:1摩尔比混合得到全氟庚酸铵盐作为乳化剂分散法制备经六氟丙烯、三氟氯乙烯、三氟乙烯修饰的聚四氟乙烯,步骤如下: 1 mole of polyethylene obtained perfluoroheptyloxy ratio of ammonium salt as an emulsifier dispersion prepared by Method hexafluoropropylene, chlorotrifluoroethylene, trifluoroethylene modifications: [0108] perfluoroheptanoic acid with ammonia according to Example 1 of the Embodiment 1 tetrafluoroethylene, as follows:

[0109] (1)往2000L卧式不锈钢聚合釜内加入1400Kg去离子水,2.1kg全氟庚酸铵盐作为乳化剂,650g 丁二酸和100 kg固体石蜡;在80°C下,聚合反应釜用四氟乙烯(TFE)排空和置换三次;置换三次后,加入〇.7g溶于1L去离子水的辛基酚聚氧乙烯醚,以45 rpm速率搅拌,保持聚合反应釜温度80°C,充入四氟乙烯单体将压力提高至1.5 MPa,将8 g溶于1000ml去离子水的引发剂过硫酸铵(APS)以100 ml/分钟速度加入;加入引发剂后聚合反应开始; [0109] (1) was added to 2000L horizontal stainless steel polymerization kettle 1400Kg of deionized water, 2.1kg of ammonium salt of perfluoro heptane as an emulsifier, 650g of succinic acid and 100 kg of solid paraffin; at 80 ° C, the polymerization reaction purged with tetrafluoroethylene (TFE) and evacuated three times replacement; was substituted three times, added 〇.7g dissolved in 1L of deionized water, polyoxyethylene octylphenol ether, stirred at a rate of 45 rpm, to maintain polymerization temperature 80 ° C, charged with tetrafluoroethylene monomer to increase the pressure to 1.5 MPa, the initiator, 8 g was dissolved in 1000ml deionized water, ammonium persulfate (APS) was added to 100 ml / min rate; polymerization initiator added after the start;

[0110] (2)反应开始1.0小时后,加入1000g六氟丙烯,1500g三氟氯乙烯和20g三氟乙烯,冲入四氟乙烯(TFE)升高压力至2.7 MPa并保持该压力; [0110] (2) 1.0 hours after the start of the reaction, was added 1000g of hexafluoropropylene, chlorotrifluoroethylene and 1500g 20g trifluoroethylene, into the tetrafluoroethylene (TFE) to 2.7 MPa and increasing the pressure to maintain the pressure;

[0111] 反应4.5小时后,将温度升高至100°C同时停止加入四氟乙烯(TFE);当压力降至0.4MP时反应结束; [0111] After 4.5 hours the reaction, the temperature was raised to 100 ° C while tetrafluoroethylene was stopped (of TFE); when the reaction pressure was reduced 0.4MP;

[0112] (3)反应完成后,分散液经凝聚、水洗和干燥得到615kg含氟聚合物分散树脂粉末。 After completion of [0112] (3) the reaction, the dispersion coagulated, washed with water and dried to obtain a fluorine-containing polymer dispersion resin powder 615kg.

[0113] 乳液中含氟聚合物浓度30.7wt%,平均粒子尺寸242nm。 [0113] The fluorine-containing emulsion polymer concentration 30.7wt%, an average particle size of 242nm. 分散树脂粉末粒子尺寸650 微米,SSG 是2.171。 Dispersing resin powder particle size of 650 microns, SSG is 2.171.

[0114] 在压缩比1600:1的模具中对得到的树脂进行挤出试验,挤出压力为47.5Mpa。 [0114] In the compression ratio of 1600: 1 in the mold resin was extrusion test, the extrusion pressure of 47.5Mpa. 挤出棒平直,洁净,表面光滑,弹性适宜。 Extruded rods straight, clean, smooth surface, suitable elasticity.

Claims (10)

  1. 1.一种含氟聚合反应的低毒性乳化剂,其特征在于,该乳化剂是由全氟庚酸或全氟庚酸盐提纯制得,通式为CF3(CF2)5C00M,Μ为H、L1、Na、K或NH4离子中的一种;其中,结构为CF3 (CF2) nCOOM,n^6的整数,的杂质总含量< lwt %,且结构为CF3 (CF2) nCOOM, Ο < m彡4的整数,的杂质总含量彡lwt%。 1. A fluorine-containing polymerizable emulsifier of low toxicity reaction, wherein the emulsifier is prepared from perfluoro heptanoic acid or perfluoro heptanoate purification system, the formula CF3 (CF2) 5C00M, Μ is H, L1, Na, K or one NH4 ions; wherein the structure CF3 (CF2) nCOOM, n ^ is an integer of 6, the total impurities <lwt%, and the structure of CF3 (CF2) nCOOM, Ο <m San 4 is an integer, the total impurities San lwt%.
  2. 2.根据权利要求1所述的含氟聚合反应的低毒性乳化剂,其特征在于,所述的乳化剂中结构为CF3(CF2)nC00M,n ^ 6的整数,的杂质总含量< 0.5wt%,且结构为CF3 (CF^COOM,0彡m彡4的整数,的杂质总含量彡0.5wt%。 The low toxicity of the polymerization the fluorinated emulsifier of claim 1, wherein said emulsifier structure CF3 (CF2) nC00M, n ^ is an integer of 6, a total content of impurities <0.5wt %, and the structure CF3 (CF ^ COOM, m an integer of 0 San San 4, the total content of impurities San 0.5wt%.
  3. 3.根据权利要求2所述的含氟聚合反应的低毒性乳化剂,其特征在于,所述的乳化剂中结构为CF3(CF2)nC00M,n ^ 6的整数,的杂质总含量< 0.lwt %,且结构为CF3 (CF^COOM,0彡m彡4的整数,的杂质总含量彡0.lwt %。 According to claim 2, wherein the fluorine-containing emulsifier of low toxicity polymerization reaction, wherein said emulsifier structure CF3 (CF2) nC00M, the integer n ^ 6, the total content of impurities <0. lwt%, and the structure CF3 (CF ^ COOM, m an integer of 0 San San 4, the total content of impurities San 0.lwt%.
  4. 4.根据权利要求1所述的含氟聚合反应的低毒性乳化剂,其特征在于,所述的乳化剂中碘和碘化合物总含量< 50ppm。 The fluorine-containing emulsifier of claim 1 low toxicity polymerization claim, wherein the total content of the emulsifier iodine and iodine compounds <50ppm.
  5. 5.根据权利要求4所述的含氟聚合反应的低毒性乳化剂,其特征在于,所述的乳化剂中碘和碘化合物总含量< lppm。 The fluorine according to claim 4, wherein the polymerization reaction is low toxic emulsifiers, wherein the emulsifiers in the total content of iodine and an iodine compound <lppm.
  6. 6.权利要求1〜5任一项所述的含氟聚合反应的低毒性乳化剂应用于分散法生产含氟聚合物。 Fluorine according to any of claim 1 ~ 5 low toxicity emulsifier dispersion polymerization method applied to the production of a fluorine-containing polymer.
  7. 7.一种利用权利要求1〜5任一项所述的含氟聚合反应的低毒性乳化剂制备含氟聚合物的方法,步骤如下: (1)搅拌条件下向聚合反应釜中加入水、含氟聚合反应的低毒性乳化剂,加热聚合反应釜至50〜150°C,然后加入水重量0.1〜500ppm的引发剂引发聚合反应; 所述的含氟聚合反应的低毒性乳化剂加入量为水重量的0.01%〜1% ; 所述的引发剂包括过硫酸铵、过硫酸钾、过氧化叔丁基异丙苯、过氧化苯甲酰、偶氮二异丁腈、高锰酸钾、过氧化琥珀酸、过硫酸钾和亚硫酸钠的氧化还原体系、过硫酸钾和硫酸氢钠和硫酸亚铁的氧化还原体系、过硫酸钾和硫酸氢钠和硝酸银的氧化还原体系; (2)连续通入含氟单体维持聚合反应釜压力恒定,所述恒定压力大小为0.3〜.7.0MPa ; (3)反应完成后,将反应乳液中的含氟聚合物凝聚分离、水洗涤、干燥,即得固态含氟聚合物; 或者 A method according to any of claim 1 ~ 5 using the low toxicity of the fluorinated emulsifier in the polymerization reaction of a fluorine-containing polymer of any one of the claims, the following steps: (1) with stirring to the polymerization kettle was added water, low toxicity fluorinated emulsifier polymerization reaction, the polymerization reactor was heated to 50~150 ° C, then water 0.1~500ppm by weight of polymerization initiators; emulsifier added amount of the low toxicity of the fluorine-containing polymer is the reaction 0.01% ~ 1% by weight of water; the initiator include ammonium persulfate, potassium persulfate, t-butyl cumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, potassium permanganate, peroxide succinic acid, potassium persulfate and sodium sulfite redox system, potassium persulfate and sodium bisulfite and ferrous sulfate redox system, potassium persulfate and sodium hydrogen sulfate and silver nitrate redox system; (2) continuously into the fluorine-containing monomer to maintain a constant pressure in the polymerization reactor, the size of the constant pressure 0.3~.7.0MPa; after completion (3) the reaction, the emulsion was coagulation washed fluoropolymer separated, water, and dried to obtain a solid fluoropolymers; or 对反应完的乳液进行浓缩,至浓缩液中含氟聚合物的浓度为30%〜70wt%,SP得含氟聚合物浓缩液。 After the reaction emulsion was concentrated to a concentration in the fluoropolymer concentrate for 30% ~70wt%, SP obtained fluoropolymer concentrate.
  8. 8.根据权利要求7所述的制备含氟聚合物的方法,其特征在于,所述的步骤(1)中加热聚合反应釜之前再加入水重量的0.1〜12%的石蜡、水重量0.01〜0.1%的丁二酸、0.1〜.10g辛基酚聚氧乙烯醚; 加入引发剂之前反复充入抽出四氟乙烯至聚合反应釜的氧气含量< 30ppm。 8. The method according to claim 7 of making a fluoropolymer, characterized in that the paraffin 0.1~12% by weight of water was added prior to the polymerization step of heating said reactor (1), the weight of water 0.01~ 0.1% succinic acid, 0.1~.10g polyoxyethylene octylphenol ether; repeatedly charged before addition of the initiator to the polymerization of tetrafluoroethylene extracting oxygen content <30ppm kettle.
  9. 9.根据权利要求7所述的制备含氟聚合物的方法,其特征在于,所述的步骤(2)中含氟单体为四氟乙烯、偏氟乙烯、三氟氯乙烯、六氟丙烯或全氟烷基乙烯基醚中的一种或几种混入口ο 9. A process for preparing a fluorine-containing polymer according to claim 7, wherein said step (2) is a fluorine-containing monomer is tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, hexafluoropropylene or one or more perfluoroalkyl vinyl ether mixed inlet ο
  10. 10.一种利用权利要求1〜5任一项所述的含氟聚合反应的低毒性乳化剂制备聚四氟乙烯的方法,步骤如下: (1)搅拌条件下向聚合反应釜中加入水、含氟聚合反应的低毒性乳化剂、石蜡、丁二酸和辛基酚聚氧乙烯醚,加热聚合反应釜至50〜150°C, 所述的含氟聚合反应的低毒性乳化剂加入量为水重量的0.01%〜1% ; 所述的石蜡加入量为水重量的0.1〜12% ; 所述的丁二酸加入量为水重量的0.01〜0.1% ; 所述的辛基酚聚氧乙烯醚加入量为0.7g ; 当温度达到60〜85°C时,对聚合反应釜进行抽空后,反复充入抽出四氟乙烯至聚合反应爸内氧含量< 30ppm ; 然后加入水重量0.1〜500ppm的引发剂引发聚合反应; 所述的引发剂包括过硫酸铵、过硫酸钾、过氧化叔丁基异丙苯、过氧化苯甲酰、偶氮二异丁腈、高锰酸钾、过氧化琥珀酸、过硫酸钾和亚硫酸钠的氧化还原体系、过硫酸钾和硫酸 The method of low toxicity emulsifier polytetrafluoroethylene claim 10. A use of a fluorine-containing polymerization according to any of 1 ~ 5, the following steps: (1) with stirring to the polymerization kettle was added water, fluorinated emulsifier polymerization of low toxicity, paraffins, succinic acid and polyoxyethylene octylphenol ether, the polymerization reactor was heated to 50~150 ° C, the emulsifier added amount of the low toxicity of the fluorine-containing polymer is the reaction 0.01% ~ 1% by weight of water; said paraffin is added in an amount of 0.1~12% by weight of water; the succinic acid is added in an amount of 0.01~0.1% by weight of water; the polyoxyethylene octylphenol ether was added in an amount of 0.7 g; when the temperature reached 60~85 ° C, after the polymerization kettle was evacuated repeatedly charged oxygen content in the drawn tetrafluoroethylene to the polymerization reaction dad <30ppm; by weight of water was then added 0.1~500ppm polymerization initiators; the initiator include ammonium persulfate, potassium persulfate, t-butyl cumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, potassium permanganate, peroxide, succinic acid, potassium persulfate and sodium sulfite redox system, potassium persulfate and sulfuric acid 氢钠和硫酸亚铁的氧化还原体系、过硫酸钾和硫酸氢钠和硝酸银的氧化还原体系; (2)连续通入四氟乙烯维持聚合反应釜压力恒定,所述恒定压力大小为(λ 3〜.7.0MPa ; (3)反应完成后,将反应乳液中的含氟聚合物凝聚分离、水洗涤、100〜200°C干燥,即得固态聚四氟乙烯; 或者,对反应完的乳液进行浓缩,至浓缩液中含氟聚合物的浓度为30%〜70wt%;即得聚四氟乙烯浓缩液。 Sodium and ferrous sulfate redox system, potassium persulfate and sodium bisulfite, and silver nitrate redox system; (2) of tetrafluoroethylene was continuously fed to maintain a constant pressure in the polymerization reactor, the pressure is constant size ([lambda] 3~.7.0MPa; after completion (3), the reaction emulsion fluoropolymer coagulation was separated, washed with water, 100~200 ° C and dried to obtain a solid polytetrafluoroethylene; or, on completion of the reaction emulsion concentrated and to the concentrate concentration in the fluorine-containing polymer is 30% ~70wt%; polytetrafluoroethylene to obtain a concentrate.
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